KR100369118B1 - High density ceramic thick film fabrication method by screen printing - Google Patents
High density ceramic thick film fabrication method by screen printing Download PDFInfo
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- KR100369118B1 KR100369118B1 KR10-2000-0025622A KR20000025622A KR100369118B1 KR 100369118 B1 KR100369118 B1 KR 100369118B1 KR 20000025622 A KR20000025622 A KR 20000025622A KR 100369118 B1 KR100369118 B1 KR 100369118B1
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- 239000000919 ceramic Substances 0.000 title claims abstract description 30
- 238000007650 screen-printing Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000059 patterning Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 2
- 229940088601 alpha-terpineol Drugs 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- 229910020698 PbZrO3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/06—Coating on selected surface areas, e.g. using masks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
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- Structural Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
본 발명은 스크린 프린팅에 의한 고밀도 세라믹후막 제조방법에 관한 것으로, 세라믹 후막을 제조하는데 있어서 패터닝이 따로 필요없고 원하는 패턴 크기의 후막을 직접 형성할 수 있는 장점을 가진 스크린 프린팅 방법으로 후막을 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a high density ceramic thick film by screen printing, the method of manufacturing a thick film by the screen printing method having the advantage that can be directly formed a thick film of the desired pattern size without the need for patterning separately in the manufacture of ceramic thick film It is about.
스크린 프린팅 방법으로 세라믹 후막을 제조할 때 커다란 문제점중의 하나는 치밀화가 어렵다는 점이다. 이를 극복하기 위하여 스크린 프린팅 공정을 위한 페이스트 제조시 입자와 입자 사이에 열처리 공정중 쉽게 융해되어 채울 수 있는 유리상을 첨가하거나, 열처리시 가압열처리를 함으로써 치밀화를 도모하기도 한다.One of the major problems when manufacturing ceramic thick films by screen printing is the difficulty in densification. In order to overcome this problem, in the preparation of a paste for screen printing process, a glass phase that can be easily melted and filled during the heat treatment process is added between the particles and the particles, or densified by pressurized heat treatment during the heat treatment.
압전 및 초전 특성을 가지고 있어 마이크로 디바이스에 이들 특성을 적용하기 위한 많은 연구가 이루어지고 있는 세라믹 재료의 하나인 Pb(Zr,Ti)O3(PZT)의 경우를 예로 들어 설명하면, 후막을 형성하기 위하여 Koch 등은 페이스트에 유리상인 5% lead borosilicate glass 를 첨가하여 후막을 제조하는 연구를 하였고[Sensros and Actuators A, 70 (1998) 98-103], Chen 등은 4% Li2CO3와 Bi2O3를 첨가하여 유리상을 형성시켜 치밀화와 저온소성의 두가지 목적을 달성하기 위한 연구를 수행하였다[J. of Appl. Phys, 77(1995) 3349-3353]. 또한 Yao 등은 스크린 프린팅후 isostatic pressing을 가하여 알루미나 기판위에 PZT 후막의 치밀화를 도모하기 위한 연구를수행하기도 하였지만[Sensros and Actuators A, 71 (1998) 139-143], 열처리 온도가 1130℃로 높아 Si 웨이퍼위에 막을 형성하는 마이크로 디바이스 소자 응용에 제약이 되고 있다.In the case of Pb (Zr, Ti) O 3 (PZT), one of the ceramic materials having piezoelectric and pyroelectric properties and many researches for applying these properties to microdevices has been described as an example, forming a thick film To this end, Koch et al. Studied the manufacture of thick films by adding 5% lead borosilicate glass as a glass phase to pastes [Sensros and Actuators A, 70 (1998) 98-103], and Chen et al., 4% Li 2 CO 3 and Bi 2. O 3 was added to form a glass phase, and studies were carried out to achieve two purposes of densification and low temperature baking. of Appl. Phys, 77 (1995) 3349-3353. Yao et al. Also conducted studies to increase the density of PZT thick films on alumina substrates by isostatic pressing after screen printing [Sensros and Actuators A, 71 (1998) 139-143]. There is a limitation in the application of micro device devices for forming a film on a wafer.
또 다른 치밀화 방법의 하나로, 같은 재료로 만들어진 졸을 이용하여 세라믹 분말과 섞어 후막을 제조함으로써 첨가된 졸이 입자 사이의 빈 공간을 채워주어 보다 치밀한 막을 제조하는 방법이 있다. 이러한 시도는 Barrow등에 의하여 이루어 졌으며 그들은 PZT 분말과 PZT 졸을 섞어 후막을 형성하여 650℃의 낮은 온도에서 20㎛ 정도의 막을 증착하였다.[J. of Appl. Phys, 81(1997) 876-881] 그러나 이러한 방법은 증착후 적당한 마스크를 이용하여 패터닝을 한후 에칭하여 원하는 크기로 패터닝하는 후 공정이 요구되고, 졸을 이용하여 코팅하는 동안에 졸과 세라믹 입자 사이의 분리에 의하여 균일한 막을 형성하는데 제약이 따른다.Another method of densification is to prepare a thicker film by mixing a ceramic powder with a sol made of the same material to prepare a thick film, thereby adding a more compact sol to fill the void space between the particles. This attempt was made by Barrow et al. They mixed PZT powder with PZT sol to form a thick film and deposited a film of about 20 μm at a low temperature of 650 ° C. [J. of Appl. Phys, 81 (1997) 876-881] However, this method requires a post-deposition patterning using a suitable mask, followed by etching and patterning to a desired size, and between sol and ceramic particles during coating with sol. There is a restriction in forming a uniform film by separation.
본 발명의 목적은 패터닝 공정이 따로 필요한 종래 기술의 복잡함을 해소하면서 기존의 프린팅 방법으로 저온에서 보다 치밀한 세라믹 후막을 제조하기위한 방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing denser ceramic thick films at low temperatures with existing printing methods while eliminating the complexity of the prior art, which requires a separate patterning process.
도 1은 본 발명의 방법에 의하여 제조한 세라믹 후막의 단면을 보여주는 SEM 사진이다.1 is a SEM photograph showing a cross section of a ceramic thick film prepared by the method of the present invention.
도 2는 본 발명의 방법에 의하여 제조 세라믹후막의 XRD 그래프이다.2 is an XRD graph of a ceramic thick film prepared by the method of the present invention.
도 3a 및 3b는 본 발명의 방법에 의하여 제조한 세라믹 후막의 P-E 전기적 특성을 나타낸 그래프이다.3A and 3B are graphs showing P-E electrical characteristics of a ceramic thick film prepared by the method of the present invention.
본 발명은 유기 바인더 및 용제로 구성된 비이클(Vehicle)을 제조하고, 상기 비이클에 세라믹 분말을 분산시켜 페이스트(paste)를 제조하고, 상기 페이스트로 스크린 프린팅법에 의해 일정한 두께의 후막을 프린팅하고, 프린팅된 후막을 건조한 후 유기바인더를 제거하고, 프린팅된 후막 표면에 졸(sol) 또는 졸과 유사한 용액(solution)을 도포하여 상기 후막으로 스며들도록 함침시키고, 상기 후막을 스피닝(spinning)하여 여분의 졸 또는 졸과 유사한 용액을 제거하고, 상기 후막을 건조하여 중간 열처리를 하고, 상기 후막을 소결하는 단계를 포함하여 이루어지는 스크린 프린팅에 의한 고밀도 세라믹후막 제조방법을 제공한다.The present invention is to prepare a vehicle (Vehicle) composed of an organic binder and a solvent, to disperse the ceramic powder in the vehicle to prepare a paste (paste), and to print a thick film of a constant thickness by screen printing method with the paste, printing After the dried thick film is dried, the organic binder is removed, a sol or a sol-like solution is applied to the printed thick film surface to impregnate the thick film, and the thick film is spun to give extra sol. Or removing a sol-like solution, drying the thick film to perform an intermediate heat treatment, and sintering the thick film, thereby providing a method of manufacturing a high density ceramic thick film by screen printing.
상기 졸과 유사한 용액은 PZT성분을 함유한 알콕사이드(alkoxide), 수화물(hydrate), 카보네이트(carbonate) 등의 금속유기물(metal organic) 등을 단독으로, 혼합된 상태로, 또는 용매에 단순히 용해시킨 용액을 포함한다.The sol-like solution is a solution in which metal organic matters such as alkoxide, hydrate, and carbonate containing PZT components are alone, mixed, or simply dissolved in a solvent. It includes.
상기 졸 또는 졸과 유사한 용액은 상기 세라믹 분말과 동일한 성분을 사용할 수도 있고, 상기 세라믹 분말과 다른 성분을 사용하는 것도 가능하다. 상기 소결시 소결온도는 700 ~ 1200℃의 범위이며, 바람직하게는 800 ~ 900℃의 범위이고, 프린팅된 후막의 두께는 1 ~ 200㎛의 범위이다.The sol or a solution similar to the sol may use the same component as the ceramic powder, or may use a different component from the ceramic powder. The sintering temperature during the sintering is in the range of 700 ~ 1200 ℃, preferably in the range of 800 ~ 900 ℃, the thickness of the printed thick film is in the range of 1 ~ 200㎛.
한편, 스크린 프린팅에 의해 일정 두께의 후막을 형성하고 졸 또는 졸과 유사한 용액을 후막 표면에 함침시키는 과정은 반복적으로 실시함으로써 상기 후막을 더욱더 치밀화 시킬 수 있다.Meanwhile, the thick film may be further densified by repeatedly forming a thick film by screen printing and impregnating a sol or a sol-like solution on the thick film surface repeatedly.
후막 표면에 도포되는 졸 또는 졸과 유사한 용액은 후막의 소결 전에 도포할 수도 있지만, 소결 후에 도포하는 것도 가능하며, 소결 전과 소결 후에 각각 도포할 수도 있다. 상기 후막을 소결한 후에 졸 또는 졸과 유사한 용액을 도포하는 경우 최종 소결은 600 ~ 700℃의 온도에서 수행한다.The sol or sol-like solution applied to the thick film surface may be applied before sintering the thick film, but may also be applied after sintering, or may be applied before and after sintering, respectively. When sol or a sol-like solution is applied after sintering the thick film, the final sintering is carried out at a temperature of 600 ~ 700 ℃.
이하 본 발명의 특징과 구체적인 내용을 실시예를 통하여 설명하면 다음과 같다.Hereinafter, the features and specific details of the present invention will be described with reference to the following examples.
실시예 1Example 1
세라믹후막 제조에 있어서 스크린 프린팅법을 적용하기 위해서는 코팅하려는 원료로 이루어진 페이스트(Paste)를 준비해야 한다. PZT 페이스트 경우는 일반적으로 유기 바인더 및 용제로 구성된 비이클(Vehicle)에 특성 구현 물질인 PZT 분말을 혼합, 분산시키는 과정을 통하여 제조된다.In order to apply the screen printing method in the manufacture of a ceramic thick film, a paste made of a raw material to be coated should be prepared. The PZT paste is generally manufactured by mixing and dispersing PZT powder, which is a material implementing material, in a vehicle composed of an organic binder and a solvent.
본 발명에서는 이러한 페이스트 제조에 있어서 일반적인 성분 이외에 새로이 PZT졸(Sol)을 첨가하였다. 이 졸은 통상적인 졸 제조 공정일 수도 있고, 특정 목적을 달성하기 위하여 다른 조성의 졸을 첨가하기도 한다. 예를 들면 고온에서 열처리 하므로 여분의 PbO가 5 ~ 20% 첨가되어지기도 하고, 성분중 Zr/Ti의 비가 다른 졸을 제조하기도 한다. PZT는 PbTiO3와 PbZrO3의 고용체(solid solution)로서 Zr/Ti의 비에 따라 특성이 변화하고, 압전특성이나 유전특성은 Zr/Ti의 비가 52mol%/48mol%인 경우 최대가 되지만, 사용목적에 따라서 Zr/Ti의 비를 변화시켜 특성의 변화를 도모할 수 있다.In the present invention, PZT sol (Sol) was newly added in addition to the general ingredient in preparing such a paste. This sol may be a conventional sol preparation process, or sol of different composition may be added to achieve a specific purpose. For example, heat treatment at a high temperature may add 5 to 20% of excess PbO, and may also prepare a sol having a different Zr / Ti ratio in the components. PZT is a solid solution of PbTiO3 and PbZrO3 whose properties change with the ratio of Zr / Ti, and the piezoelectric and dielectric properties are maximum when the ratio of Zr / Ti is 52 mol% / 48 mol%, but depending on the purpose of use The characteristics can be changed by changing the ratio of Zr / Ti.
제조과정은 먼저 비이클을 제조하며, 이때 비이클은 일반적으로 페이스트의 용제(Solvent)로서 널리 적용되고 있는 α-terpineol를 기본으로 하여 여기에 BEEA(butoxy ethoxy ethyl acetate), PVB(polyvinyl butyral) 및 PEG(polyethylene glycol)등의 수지를 완전히 용해시켜 제조하였다. 이 비이클에 PZT 분말 및 PZT 졸을 혼합하고 분산하여 페이스트를 제조하였다.The manufacturing process first manufactures a vehicle, which is based on α-terpineol, which is generally applied as a solvent for pastes, and is based on butoxy ethoxy ethyl acetate (BEEA), polyvinyl butyral (PVB), and PEG (PEG). It was prepared by completely dissolving a resin such as polyethylene glycol). PVT powder and PZT sol were mixed and dispersed in this vehicle to prepare a paste.
PZT 분말은 통상적인 파우더 제조 공정에 의하여 제조되어진다. 즉 습식 믹싱 방법으로 원료 분말을 24시간 볼 밀링에 의하여 혼합하고 건조후 하소하여 반응성을 높였으며, 어트리션밀링(attrition milling)에 의해 분쇄하여 입자크기가 0.3㎛ 이하가 되도록 준비하였다.PZT powders are prepared by conventional powder preparation processes. That is, the raw powder was mixed by dry milling for 24 hours by ball milling and calcined after drying to increase the reactivity. The powder was pulverized by attrition milling to prepare a particle size of 0.3 μm or less.
페이스트 제조시 혼합, 분산과정에 사용한 방법은 볼밀링(Ball milling) 및 3본롤밀링(Three roll milling)을 적용하였으며, 이때 제조된 페이스트의 PZT분말 함량은 50wt% ~ 85wt%이고, 비이클의 함량은 10wt% ~ 25wt%이며, PZT 졸의 함량은 5wt% ~ 25wt%이다.The ball milling and three roll milling methods were used for mixing and dispersing the paste, and the PZT powder content of the prepared paste was 50 wt% to 85 wt%, and the content of the vehicle was 10 wt% to 25 wt%, and PZT sol content is 5 wt% to 25 wt%.
이렇게 제조한 페이스트를 사용하여 통상적인 스크린 프린팅법으로 후막을 프린팅하고 건조한 후, 이를 700 ~ 1200℃의 온도에서 소결하여 후막을 제조하였다.The thick film was printed and dried using a conventional screen printing method using the paste thus prepared, followed by sintering at a temperature of 700 to 1200 ° C. to prepare a thick film.
실시예 1은 종래 기술과 비교해볼 때, 종래 기술이 PZT분말에 PZT졸을 혼합하여 페이스트를 제조하므로 페이스트의 점도가 낮아 스크린 인쇄에는 적합하지 않고 dip coating이나 spin coating에 적용하고 있으나, 실시예 1에 의한 본 발명의 경우 PZT분말과 PZT졸 이외에 비이클을 함께 혼합하여 페이스트의 점도를 스크린 인쇄법에 적용할 수 있도록 조절할 수 있으며 또한 페이스트 내의 PZT분말의 분산성을 향상시킬 수 있다.Compared with the prior art, Example 1 is a paste prepared by mixing PZT sol with PZT powder, so that the viscosity of the paste is not suitable for screen printing and is applied to dip coating or spin coating. In the case of the present invention by mixing the vehicle in addition to the PZT powder and PZT sol can be adjusted to apply the viscosity of the paste to the screen printing method and can also improve the dispersibility of the PZT powder in the paste.
실시예 2Example 2
실시예 1과 동일하게 α-terpineol를 기본으로 하여 여기에 BEEA(butoxy ethoxy ethyl acetate), PVB(polyvinyl butyral) 및 PEG(polyethylene glycol)등의 수지를 완전히 용해시켜 비이클을 제조하였다. 여기에 PZT 분말을 혼합, 분산시켜 졸이 포함되지 않은 PZT 페이스트를 제조하여 스크린 프린팅법으로 원하는 두께의후막을 프린팅한다. 이를 건조한 후 400 ~ 700℃의 온도에서 유기바인더를 제거(Burn-out)시켰다. 그 다음에 프린팅된 후막 표면에 PZT 졸액을 도포하여 PZT 졸이 후막으로 스며들도록 함침시킨다. 이후 후막을 스피닝(spinning)하여 여분의 PZT 졸을 제거하고 80 ~ 600℃의 온도에서 건조 및 중간 열처리를 한 후, 700 ~ 1200℃의 온도에서 소결하여 후막을 제조하였다.As in Example 1, a vehicle was prepared by completely dissolving a resin such as BEEA (butoxy ethoxy ethyl acetate), PVB (polyvinyl butyral), and PEG (polyethylene glycol) based on α-terpineol. PZT powder is mixed and dispersed therein to prepare a PZT paste containing no sol, and a thick film having a desired thickness is printed by screen printing. After drying, the organic binder was removed (Burn-out) at a temperature of 400 ~ 700 ℃. The PZT sol solution is then applied to the printed thick film surface to impregnate the PZT sol into the thick film. Thereafter, the thick film was spun to remove excess PZT sol, dried and intermediate heat treated at a temperature of 80 to 600 ° C., and then sintered at a temperature of 700 to 1200 ° C. to prepare a thick film.
실시예 3Example 3
실시예 1에 의해 제조한 졸을 함유한 페이스트를 이용하여 후막을 원하는 두께로 프린팅한다. 이후 실시예 2처럼 이를 건조한 후 400 ~ 700℃의 온도에서 유기용매를 제거(Burn-out)시킨다. 그 다음에 프린팅된 후막 표면에 PZT 졸을 도포하여 PZT 졸액이 후막으로 스며들도록 함침시킨다. 이후 시편을 스피닝하여 여분의 PZT 졸액을 제거하고 80 ~ 600℃의 온도에서 건조 및 중간 열처리를 한후, 이를 700 ~ 1200℃의 온도에서 소결하여 후막을 형성한다.The thick film is printed to a desired thickness using the paste containing the sol prepared in Example 1. Then, after drying it as in Example 2 to remove the organic solvent (Burn-out) at a temperature of 400 ~ 700 ℃. The PZT sol is then applied to the printed thick film surface to impregnate the PZT sol liquid into the thick film. Thereafter, the specimen is spun to remove excess PZT sol solution, dried and intermediate heat treated at a temperature of 80 to 600 ° C., and then sintered at a temperature of 700 to 1200 ° C. to form a thick film.
실시예 4Example 4
실시예 2 및 3과 동일한 방법으로 후막을 증착하지만, 원하는 두께가 되도록 반복 스크린 프린팅하는데 있어서 매회 스크린 프린팅 후 표면에 졸을 도포 함침시키는 공정을 실시예 2 및 3에서의 방법과 동일하게 되풀이 함으로써 막을 치밀화시켰다.The thick film is deposited in the same manner as in Examples 2 and 3, but in the repeated screen printing so as to have a desired thickness, the film is formed by repeating the same process as in Examples 2 and 3, after each screen printing, by applying a sol to the surface. Densified.
실시예 5Example 5
실시예 1, 2에 있어서 PZT 후막 제조를 위한 원료 준비과정에서 PbO를 5 ~ 20% 추가하여 후막증착을 위한 페이스트를 제조하였다.In Examples 1 and 2, a paste for thick film deposition was prepared by adding 5 to 20% of PbO in preparing a raw material for preparing a PZT thick film.
PbO가 추가되는 이유는 첫째, PZT의 열처리시 PbO 성분의 증발이 일어나 PZT 내의 PbO손실이 일어난다고 알려져 있으므로 이것을 보충하기 위한 것이고, 둘째, PbO의 첨가에 의하여 액상소결이 촉진되고 이에 따라 PZT의 소결온도를 낮출 수 있기 때문이다.The reason for the addition of PbO is to supplement the PbO loss in the PZT because the PbO component evaporates during the heat treatment of PZT. This is because the temperature can be lowered.
이상과 같은 방법에 의하여 형성한 PZT 후막의 단면 사진이 도 1에 나타나 있다. 이 때 막 두께는 25㎛이었다. 도 2는 본 발명에 의해 제조된 세라믹 후막의 XRD 그래프로서, 800℃의 낮은 열처리 온도에도 불구하고 우수한 결정상을 보유한 막이 증착 되었음을 보여주고 있다.The cross-sectional photograph of the PZT thick film formed by the above method is shown in FIG. At this time, the film thickness was 25 µm. 2 is an XRD graph of a ceramic thick film prepared according to the present invention, showing that a film having a good crystal phase was deposited despite a low heat treatment temperature of 800 ° C.
표 1은 일반적인 스크린 프린팅 방법에 의하여 제조한 막과 졸처리 하여 증착한 막의 압전특성(d33)값을 나타낸 것으로 졸을 함침시킴으로써 압전상수값의 증가가 거의 2 ~ 3 배에 이름을 알 수 있다.Table 1 shows the piezoelectric properties (d 33 ) values of the films prepared by the general screen printing method and the films deposited by sol treatment. The name of the piezoelectric constant is increased by 2 to 3 times by impregnating the sol. .
도 3a 및 3b는 본 발명에 의해 제조된 후막의 전기적 특성중 대표적인 분극(Polarization: P) - 전계(E)의 관계를 나타낸 그래프로서, 잔류분극이 15μC/cm2의 높은 값을 갖는 후막이 형성됨을 알 수 있다.Figure 3a and 3b is a graph showing the relationship between the polarization (Polarization: P)-the electric field (E) of the electrical properties of the thick film prepared by the present invention, a thick film having a high value of 15μC / cm 2 residual polarization is formed It can be seen.
본 발명에 의하면 패터닝 공정이 필요없이 기존의 스크린 프린팅 방법을 이용하여 저온에서 보다 치밀한 세라믹 후막을 원하는 패턴 크기로 제조하는 것이 가능하다. 따라서 저온소결 및 후막의 치밀화로 인하여 압전 소자및 초전 소자 등의 마이크로 디바이스 제조에 유용하게 이용될 수 있다.According to the present invention, it is possible to manufacture a denser ceramic thick film in a desired pattern size at a low temperature by using a conventional screen printing method without the need for a patterning process. Therefore, low temperature sintering and thickening of the thick film can be usefully used in the manufacture of micro devices such as piezoelectric elements and pyroelectric elements.
Claims (9)
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KR10-2000-0025622A KR100369118B1 (en) | 2000-05-13 | 2000-05-13 | High density ceramic thick film fabrication method by screen printing |
EP01915880A EP1285102B1 (en) | 2000-05-13 | 2001-03-16 | High density ceramic thick film fabrication method by screen printing |
DE60134737T DE60134737D1 (en) | 2000-05-13 | 2001-03-16 | PREPARATION OF A HIGH-DENSITY THICK CERAMIC FILM BY SCREEN PRINTING |
US10/030,531 US6749798B2 (en) | 2000-05-13 | 2001-03-16 | High density ceramic thick film fabrication method by screen printing |
JP2001584603A JP3917426B2 (en) | 2000-05-13 | 2001-03-16 | Method for producing high-density ceramic thick film by screen printing |
AT01915880T ATE400673T1 (en) | 2000-05-13 | 2001-03-16 | PRODUCING A HIGH DENSITY THICK CERAMIC FILM BY SCREEN PRINTING |
PCT/KR2001/000422 WO2001088222A1 (en) | 2000-05-13 | 2001-03-16 | High density ceramic thick film fabrication method by screen printing |
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KR100449894B1 (en) * | 2002-01-31 | 2004-09-22 | 한국과학기술원 | Embedded Capacitor Films with High Dielectric Constant and Low Tolerance Using Multimodal Power Size Distribution |
SG115500A1 (en) * | 2002-10-09 | 2005-10-28 | Inst Materials Research & Eng | Method to produce a reliable piezoelectric thick film on a substrate |
DE10350788B3 (en) * | 2003-10-29 | 2005-02-03 | Fachhochschule Kiel | Production of a ceramic layer on a substrate used e.g. in the production of gas sensors comprises mixing a ceramic powder, sol and screen printing carrier to form a screen printing paste, applying on the substrate, and further processing |
FR2871942B1 (en) * | 2004-06-17 | 2006-08-04 | Commissariat Energie Atomique | PROCESS FOR THE PREPARATION OF PIEZOELECTRIC MATERIALS |
CN1298674C (en) * | 2005-04-06 | 2007-02-07 | 清华大学 | Method for preparing piezoelectric ceramic film |
JP4940389B2 (en) * | 2007-01-19 | 2012-05-30 | 国立大学法人 名古屋工業大学 | Lead-free piezoelectric ceramic composite and piezoelectric element using the same |
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DK193287A (en) * | 1986-04-16 | 1987-10-17 | Alcan Int Ltd | COMPOSITE MEMBRANE |
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JPH04215414A (en) * | 1990-12-14 | 1992-08-06 | Taiyo Yuden Co Ltd | Manufacture of laminated ceramic electronic part |
US5432015A (en) * | 1992-05-08 | 1995-07-11 | Westaim Technologies, Inc. | Electroluminescent laminate with thick film dielectric |
JP2747881B2 (en) * | 1994-01-20 | 1998-05-06 | 大日本塗料株式会社 | Manufacturing method of three-dimensional pattern painted board for bathroom |
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US4409261A (en) * | 1980-02-07 | 1983-10-11 | Cts Corporation | Process for air firing oxidizable conductors |
JPH01112785A (en) * | 1987-10-27 | 1989-05-01 | Meidensha Corp | Manufacture of composite piezoelectric material film |
JPH0896624A (en) * | 1994-09-28 | 1996-04-12 | Murata Mfg Co Ltd | Thick film paste |
JPH08162738A (en) * | 1994-12-07 | 1996-06-21 | Murata Mfg Co Ltd | Production of thick film cu circuit board |
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US6749798B2 (en) | 2004-06-15 |
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ATE400673T1 (en) | 2008-07-15 |
JP2003533596A (en) | 2003-11-11 |
KR20010104157A (en) | 2001-11-24 |
EP1285102B1 (en) | 2008-07-09 |
WO2001088222A1 (en) | 2001-11-22 |
DE60134737D1 (en) | 2008-08-21 |
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